EP0670379A1 - Composition de traitement de surfaces en cuivre ou alliages de cuivre - Google Patents

Composition de traitement de surfaces en cuivre ou alliages de cuivre Download PDF

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Publication number
EP0670379A1
EP0670379A1 EP95102686A EP95102686A EP0670379A1 EP 0670379 A1 EP0670379 A1 EP 0670379A1 EP 95102686 A EP95102686 A EP 95102686A EP 95102686 A EP95102686 A EP 95102686A EP 0670379 A1 EP0670379 A1 EP 0670379A1
Authority
EP
European Patent Office
Prior art keywords
copper
acid
composition
compound
azole
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP95102686A
Other languages
German (de)
English (en)
Other versions
EP0670379B1 (fr
Inventor
Maki C/O Mec Co. Ltd. Arimura
Daisaku C/O Mec Co. Ltd. Akiyama
Toshiko C/O Mec Co. Ltd. Nakagawa
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
MEC Co Ltd
Original Assignee
MEC Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by MEC Co Ltd filed Critical MEC Co Ltd
Publication of EP0670379A1 publication Critical patent/EP0670379A1/fr
Application granted granted Critical
Publication of EP0670379B1 publication Critical patent/EP0670379B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/383—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by microetching
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/52—Treatment of copper or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/18—Acidic compositions for etching copper or alloys thereof
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/12—Using specific substances
    • H05K2203/121—Metallo-organic compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/12—Using specific substances
    • H05K2203/122—Organic non-polymeric compounds, e.g. oil, wax or thiol
    • H05K2203/124—Heterocyclic organic compounds, e.g. azole, furan
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H05K3/061—Etching masks
    • H05K3/064—Photoresists
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards

Definitions

  • the present invention relates to a surface treating composition for copper or copper alloy which is useful for roughening the copper or copper alloy surfaces.
  • the chemical cleaning is also used for improving solderability, for example, as a pretreatment for a solder coating step or for removing oxides from copper surfaces before soldering electronic parts.
  • An aqueous solution comprising sulfuric acid and hydrogen peroxide as major components or an aqueous solution comprising a persulfate as a major component are commonly used for the chemical cleaning.
  • solder resists are shifting from the conventional thermoset type to the UV curable type which is more excellent in forming fine line patterns. Because UV curable type solder resists are inferior in their adhesion properties to copper surfaces as compared with conventional solder resists, adhesiveness of the surfaces produced using these solder resists is insufficient. There are occasions where resist coatings come off or swell during the subsequent plating step, solder coating step, or electronic parts soldering step.
  • the object of the present invention is therefore to provide a surface treating composition for copper and copper alloys which can exhibit excellent adhesiveness to solder resists and the like and provide roughened surfaces of copper or copper alloys with adequate irregularities with deep convexes and concaves and superior solderability.
  • compositions comprising an azole compound, a copper compound which is dissolved in this composition (hereinafter referred to as a dissolvable copper compound), an organic or inorganic acid, and a halogen ion, especially a composition comprising a cupric azole complex, an organic acid, and a halogen ion, can achieve this object.
  • an object of the present invention is to provide a composition for treating surfaces of copper or copper alloy which is an aqueous solution comprising: an azole compound, a dissolvable copper compound, an organic or inorganic acid, and a halogen ion.
  • said composition comprises 0.1-15% by weight of an azole compound, 0.1-5% by weight of a dissolvable copper compound as copper metal, 0.1-30% by weight of an organic or inorganic acid, and 0.01-20% by weight of a halogen ion.
  • a copper azole complex is used as said azole compound and said dissolvable copper compound.
  • said a copper azole complex is a cupric azole complex.
  • the combined use of an azole compound and a dissolvable copper compound as essential components ensures the composition of the present invention to exhibit an appropriate etching rate for surface treatments.
  • the dissolvable copper compound forms a copper complex, such as a cupric complex, with an azole compound, for example.
  • dissolvable copper compound examples include copper hydroxide and copper salts of an acid, which are hereinafter mentioned.
  • an amount of 1-15% by weight (hereinafter referred to simply as %), in terms of a cupric complex of an azole compound, is preferable in view of solubility and stability.
  • an azole compound an amount of 0.1-15% is preferable; and as a copper compound, 0.1-5% (as metal) is preferable.
  • the azole compound and the dissolvable copper compound may be added separately, or they may be added as a copper complex, e.g. a cupric complex, of an azole compound.
  • a copper complex e.g. a cupric complex
  • copper hydroxide or a copper salt of an acid may be preferably used as the cupric ion source for producing such a cupric complex of an azole compound.
  • the organic acids or inorganic acids are added to the composition of the present invention for adjusting pH and for dissolving copper produced by oxidation with the cupric complex of an azole compound or the like.
  • the organic acids are saturated aliphatic acids, such as formic acid, acetic acid, propionic acid, n-butyric acid, n-valeric acid, and caproic acid; unsaturated aliphatic acids, such as acrylic acid, crotonic acid, and iso-crotonic acid; saturated aliphatic dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and pimelic acid; unsaturated aliphatic dicarboxylic acids such as maleic acid; aromatic carboxylic acids, such as benzoic acid, phthalic acid, and cinnamic acid; hydroxy carboxylic acids, such as glycolic acid, lactic acid, malic acid, and citric acid; carboxylic acids with substitu
  • These acids also can be the source for formig said copper salts used as the dissolvable copper compound.
  • the amount of the organic or inorganic acids in the composition of the present invention is preferably in the range of 0.1-30%. If this amount is too small, the composition cannot sufficiently dissolve oxidized copper and it is difficult to obtain active copper surfaces; it is too large, dissolving stability of copper is lowered.
  • Halogen ion is used in the composition of the present invention for increasing solubility of copper and oxidizing capability of the azole compounds, thereby ensuring production of copper surfaces with superior adhesiveness and solderability.
  • Fluoride ion, chloride ion, bromide ion, or the like may be used as the halogen ion.
  • These are added to the composition as a compound which can be dissociated in a solution.
  • a compound may be an acid, such as hydrochloric acid or hydrobromic acid; a salt, such as sodium chloride, calcium chloride, potassium chloride, ammonium chloride, or potassium bromide; or a metal salt, such as copper chloride, zinc chloride, iron chloride, or tin bromide.
  • the amount of the halogen ion in the composition of the present invention is preferably in the range of 0.01-20%. If this amount is too small, it is difficult to obtain copper surfaces with excellent adhesiveness and solderability; if it is too large, dissolving stability of copper is lowered.
  • the pH of the surface treating composition of the present invention is in the range of less than 1 to about 8 depending on the kinds of organic or inorganic acids and other additives.
  • a salt of organic acid such as a sodium, potassium or ammonium salt of organic acid, may be added.
  • additives which may be added besides the above components include a complexing agent for improving dissolving stability of copper, such as ethylenediamine, pyridine, aniline, ammonia, monoethanolamine, diethanolamine, triethanolamine, and N-methyldiethanolamine; and other various additives for producing copper surfaces with excellent adhesiveness and solderability.
  • the surface treating composition can be prepared by adding the above-mentioned components, at proportions described above, to water and blending the mixture. There are no specific limitations to the method of addition. The components may be added either all at one time or separately in any arbitrary order. Ion-exchanged water is preferably used as the water.
  • the method of using the surface treating composition of the present invention includes a method of spraying the composition to the surfaces of copper or copper alloy to be treated, a method of immersing the copper or copper alloy in the composition, and the like. If necessary, air may be bubbled to oxidize cuprous ion which has formed in the composition by etching of the copper or copper alloy into to cupric ion.
  • the surface treating composition of the present invention can be widely used for chemical cleaning or the like of copper or copper alloys.
  • the resulting surfaces of copper or copper alloy have adequate irregularities with deep convexes and concaves so that they can exhibit not only excellent adhesion to resins, such as prepregs, solder resists, dry film resists, and electrodeposition resists, but also superior solderability.
  • the surface treating composition is particularly useful for the manufacture of various printed-wiring boards, including those for pin grid array (PGA) or ball grid array (BGA), as well as for the surface treatment of lead frames used for integrated circuit boards.
  • surfaces exhibiting excellent adhesion to prepregs and superior etching performance in the patterning operation can be produced by roughening copper foils using the surface treating composition of the present invention.
  • the use of the composition for roughening copper surfaces of inner layers produces surfaces which exhibit not only excellent adhesion to prepregs, but also a superb effect of preventing formation of pink rings.
  • the surfaces treated with the composition of the present invention are less glossy than the surfaces treated with conventional sulfuric acid-hydrogen peroxide etchants, it has an effect, in addition to the increased adhesion to resins, that diffusion of light during irradiation is small and resolution of photosensitive resins is thereby increased, when the photosensitive resins are coated or laminated.
  • compositions of copper or copper alloys having excellent adhesion to resins such as prepregs and resists and exhibiting superior solderability can be produced by treating these surfaces with the surface treating composition of the present invention. Because the resulting surfaces are less glossy than the surfaces produced by conventional chemical cleaning techniques, the composition of the present invention has an effect of improving resolution when the treated surfaces are used as a base for photosensitive resins. It also brings about an effect of reducing malfunctions in inspections of printed-wiring board circuits by an automatic optical inspection machine (AOI). The composition of the present invention therefore is an ideal surface treating agent for the manufacture of printed-wiring boards which are more and more miniaturized in their fine line patterns and highly integrated.
  • AOI automatic optical inspection machine

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • ing And Chemical Polishing (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)
EP95102686A 1994-03-04 1995-02-24 Procédé de micro-gravure de surfaces en cuivre ou alliages de cuivre Expired - Lifetime EP0670379B1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP3400594 1994-03-04
JP3400594 1994-03-04
JP34005/94 1994-03-04
JP200459/94 1994-08-25
JP6200459A JP2781954B2 (ja) 1994-03-04 1994-08-25 銅および銅合金の表面処理剤
JP20045994 1994-08-25

Publications (2)

Publication Number Publication Date
EP0670379A1 true EP0670379A1 (fr) 1995-09-06
EP0670379B1 EP0670379B1 (fr) 2000-05-10

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP95102686A Expired - Lifetime EP0670379B1 (fr) 1994-03-04 1995-02-24 Procédé de micro-gravure de surfaces en cuivre ou alliages de cuivre

Country Status (7)

Country Link
US (1) US5532094A (fr)
EP (1) EP0670379B1 (fr)
JP (1) JP2781954B2 (fr)
KR (1) KR950032710A (fr)
CN (1) CN1117090A (fr)
DE (1) DE69516741T2 (fr)
SG (1) SG59906A1 (fr)

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0757118A1 (fr) * 1995-08-01 1997-02-05 MEC CO., Ltd. Composition pour la micro-gravure du cuivre ou ses alliages
EP0791671A1 (fr) * 1996-02-26 1997-08-27 Shikoku Chemicals Corporation Agent de traitement de surfaces en cuivre ou ses alliages
US5800859A (en) * 1994-12-12 1998-09-01 Price; Andrew David Copper coating of printed circuit boards
EP0887439A1 (fr) * 1997-06-12 1998-12-30 Macdermid Incorporated Procédé pour améliorer l'adhérence de polymères à des surfaces métalliquesl
EP0893947A1 (fr) * 1997-07-24 1999-01-27 MEC CO., Ltd. Méthode pour le traitement de furface du cuivre ou d'alliage de cuivre
EP0926265A1 (fr) * 1997-12-19 1999-06-30 McGean-Rohco, Inc. Procédé et compositions pour la fabrication de surfaces de cuivre ayant une adhérence amélioré et articles produits à partir de ces surfaces
WO1999040765A1 (fr) * 1998-02-03 1999-08-12 Atotech Deutschland Gmbh Procede destine au pretraitement de surfaces de cuivre
WO1999040764A1 (fr) * 1998-02-03 1999-08-12 Atotech Deutschland Gmbh Solution et procede destines au pretraitement de surfaces de cuivre
EP0844809A3 (fr) * 1996-11-20 1999-12-01 Ibiden Co, Ltd. Composition d'un masque de soudure et des panneaux à circuit imprimé
EP0984672A2 (fr) * 1998-08-31 2000-03-08 MacDermid, Incorporated Procédé de traitement de surfaces métalliques
EP1031644A1 (fr) * 1999-02-25 2000-08-30 Shipley Company LLC Produits chimiques à base de thiazoles et de thiocarbamides à utiliser dans des solutions de décapage oxydantes
US6146701A (en) * 1997-06-12 2000-11-14 Macdermid, Incorporated Process for improving the adhension of polymeric materials to metal surfaces
US6162503A (en) * 1997-06-12 2000-12-19 Macdermid, Incorporated Process for improving the adhesion of polymeric materials to metal surfaces
WO2001094033A1 (fr) * 2000-06-08 2001-12-13 Macdermid, Incorporated Procede permettant d'ameliorer l'adherence de materiaux polymeres sur des surfaces metalliques
US6419784B1 (en) 2000-06-21 2002-07-16 Donald Ferrier Process for improving the adhesion of polymeric materials to metal surfaces
EP1253813A1 (fr) * 2001-04-25 2002-10-30 Mec Company Ltd. Stratifié et méthode pour sa fabrication
US6554948B1 (en) 2000-08-22 2003-04-29 Donald Ferrier Process for improving the adhesion of polymeric materials to metal surfaces
EP1500719A1 (fr) 2003-07-25 2005-01-26 Mec Company Ltd. Solution de décapage, solution de remontage et méthode pour fabriquer des cablages en cuivre
EP1565593A1 (fr) * 2002-11-26 2005-08-24 MacDermid, Incorporated Procede permettant d'ameliorer l'adherence de materiaux polymeres a des surfaces metalliques
WO2006025224A1 (fr) 2004-08-31 2006-03-09 Senju Metal Industry Co., Ltd Flux pour brasage
WO2008048240A2 (fr) * 2005-09-22 2008-04-24 Pantheon Chemical, Inc. agent chélateur de cuivre, composition comprenant l'agent et procédé de formation et d'utilisation de l'agent et de la composition
US8129151B2 (en) 1998-03-18 2012-03-06 Ajinomoto Co., Inc. L-glutamic acid-producing bacterium and method for producing L-glutamic acid
EP2514853A2 (fr) * 2011-04-18 2012-10-24 Mec Company Ltd. Composition liquide de formation de revêtement et procédé de formation de revêtement associé
CN110527996A (zh) * 2019-09-27 2019-12-03 苏州天承化工有限公司 一种棕化液及其制备方法和应用

Families Citing this family (66)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3458023B2 (ja) * 1995-08-01 2003-10-20 メック株式会社 銅および銅合金のマイクロエッチング剤
JP3458036B2 (ja) * 1996-03-05 2003-10-20 メック株式会社 銅および銅合金のマイクロエッチング剤
TW374802B (en) * 1996-07-29 1999-11-21 Ebara Densan Ltd Etching composition, method for roughening copper surface and method for producing printed wiring board
JPH1187928A (ja) * 1997-07-08 1999-03-30 Ibiden Co Ltd 多層プリント配線板
US6141870A (en) 1997-08-04 2000-11-07 Peter K. Trzyna Method for making electrical device
JP3371775B2 (ja) * 1997-10-31 2003-01-27 株式会社日立製作所 研磨方法
US6331490B1 (en) * 1998-03-13 2001-12-18 Semitool, Inc. Process for etching thin-film layers of a workpiece used to form microelectric circuits or components
JP2000064067A (ja) 1998-06-09 2000-02-29 Ebara Densan Ltd エッチング液および銅表面の粗化処理方法
CN101594747A (zh) * 1998-07-08 2009-12-02 伊比登株式会社 印刷电路板及其制造方法
CN1316175A (zh) * 1998-07-08 2001-10-03 伊比登株式会社 印刷电路板及其制造方法
EP1843650B1 (fr) 1998-09-03 2012-03-07 Ibiden Co., Ltd. Procédé de fabrication d'un panneau à circuit imprimé multicouche
US6444140B2 (en) 1999-03-17 2002-09-03 Morton International Inc. Micro-etch solution for producing metal surface topography
US6352595B1 (en) * 1999-05-28 2002-03-05 Lam Research Corporation Method and system for cleaning a chemical mechanical polishing pad
JP4063475B2 (ja) 1999-11-10 2008-03-19 メック株式会社 銅または銅合金のエッチング剤
US7351353B1 (en) 2000-01-07 2008-04-01 Electrochemicals, Inc. Method for roughening copper surfaces for bonding to substrates
US20030178391A1 (en) * 2000-06-16 2003-09-25 Shipley Company, L.L.C. Composition for producing metal surface topography
US20040099637A1 (en) * 2000-06-16 2004-05-27 Shipley Company, L.L.C. Composition for producing metal surface topography
US6447616B1 (en) 2000-08-31 2002-09-10 The Ford Meter Box Company Method for treating brass
US6432210B1 (en) 2000-08-31 2002-08-13 The Ford Meter Box Company, Inc. Method for treating brass
US6830629B2 (en) * 2000-08-31 2004-12-14 The Ford Meter Box Company, Inc. Method for treating brass
US6749691B2 (en) 2001-02-14 2004-06-15 Air Liquide America, L.P. Methods of cleaning discolored metallic arrays using chemical compositions
JP2002374066A (ja) * 2001-06-14 2002-12-26 Ibiden Co Ltd 多層プリント配線板の製造方法
JP4687852B2 (ja) 2001-06-25 2011-05-25 三菱瓦斯化学株式会社 銅および銅合金の表面処理剤
JP2003059971A (ja) * 2001-08-20 2003-02-28 Nec Kansai Ltd 配線基板及びその製造方法並びに半導体装置
JP4142312B2 (ja) * 2002-02-28 2008-09-03 ハリマ化成株式会社 析出型はんだ組成物及びはんだ析出方法
US6746547B2 (en) * 2002-03-05 2004-06-08 Rd Chemical Company Methods and compositions for oxide production on copper
KR100459271B1 (ko) * 2002-04-26 2004-12-03 엘지.필립스 엘시디 주식회사 구리 단일막 또는 구리 몰리브덴막의 식각용액 및 그식각방법
US6716281B2 (en) * 2002-05-10 2004-04-06 Electrochemicals, Inc. Composition and method for preparing chemically-resistant roughened copper surfaces for bonding to substrates
US7300601B2 (en) * 2002-12-10 2007-11-27 Advanced Technology Materials, Inc. Passivative chemical mechanical polishing composition for copper film planarization
US7232478B2 (en) 2003-07-14 2007-06-19 Enthone Inc. Adhesion promotion in printed circuit boards
JP4368161B2 (ja) * 2003-08-08 2009-11-18 日鉱金属株式会社 銅、銅合金の表面処理剤
JP3952410B2 (ja) * 2004-02-10 2007-08-01 タムラ化研株式会社 金属の表面処理剤、プリント回路基板およびプリント回路基板の金属の表面処理方法
KR100828979B1 (ko) * 2004-03-03 2008-05-14 이비덴 가부시키가이샤 에칭액, 에칭 방법 및 프린트 배선판
US7569490B2 (en) * 2005-03-15 2009-08-04 Wd Media, Inc. Electrochemical etching
US20060207890A1 (en) * 2005-03-15 2006-09-21 Norbert Staud Electrochemical etching
KR101154244B1 (ko) * 2005-06-28 2012-06-18 주식회사 동진쎄미켐 알루미늄, 몰리브덴, 인듐-틴-옥사이드를 식각하기 위한 식각액
US7393461B2 (en) * 2005-08-23 2008-07-01 Kesheng Feng Microetching solution
US7456114B2 (en) * 2005-12-21 2008-11-25 Kesheng Feng Microetching composition and method of using the same
US7875558B2 (en) * 2005-12-21 2011-01-25 Kesheng Feng Microetching composition and method of using the same
US20070221503A1 (en) * 2006-03-22 2007-09-27 Brian Larson Precoat composition for organic solderability preservative
WO2008095078A1 (fr) * 2007-01-31 2008-08-07 Advanced Technology Materials, Inc. Stabilisation de dispersions polymère-silice pour applications de pâtes pour polissage chimique mécanique
US8512504B2 (en) 2009-05-06 2013-08-20 Steven A. Castaldi Process for improving adhesion of polymeric materials to metal surfaces
WO2011010879A2 (fr) * 2009-07-23 2011-01-27 동우 화인켐 주식회사 Procédé de fabrication d’un substrat de réseau destiné à un dispositif d’affichage à cristaux liquides
US8444868B2 (en) * 2010-01-28 2013-05-21 International Business Machines Corporation Method for removing copper oxide layer
CN102834548A (zh) * 2010-04-29 2012-12-19 东友Fine-Chem股份有限公司 用于含铜和钛的金属层的蚀刻液组合物
US9763336B2 (en) 2010-07-06 2017-09-12 Atotech Deutschland Gmbh Methods of treating metal surfaces and devices formed thereby
US9345149B2 (en) 2010-07-06 2016-05-17 Esionic Corp. Methods of treating copper surfaces for enhancing adhesion to organic substrates for use in printed circuit boards
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CN103952702A (zh) * 2014-05-04 2014-07-30 深圳市实锐泰科技有限公司 蚀刻液及使用该蚀刻液进行软性线路板细线蚀刻的方法
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JP2016029681A (ja) 2014-07-25 2016-03-03 イビデン株式会社 多層配線板及びその製造方法
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JP6338232B1 (ja) * 2017-09-22 2018-06-06 メック株式会社 銅表面の粗化方法および配線基板の製造方法
US11678433B2 (en) 2018-09-06 2023-06-13 D-Wave Systems Inc. Printed circuit board assembly for edge-coupling to an integrated circuit
US11647590B2 (en) 2019-06-18 2023-05-09 D-Wave Systems Inc. Systems and methods for etching of metals
US12033996B2 (en) 2019-09-23 2024-07-09 1372934 B.C. Ltd. Systems and methods for assembling processor systems
CN115110085A (zh) * 2021-10-23 2022-09-27 赵晓峰 一种铜及合金过氧化氢化学抛光体系中改进脱膜工序的新方法
CN114457335B (zh) * 2022-02-15 2023-10-27 江西省科学院应用物理研究所 一种铜铁碳合金金相浸蚀剂及其使用方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0364132A1 (fr) * 1988-09-29 1990-04-18 Shikoku Chemicals Corporation Procédé pour former un revêtement de conversion sur une surface de cuivre ou d'un alliage de cuivre
EP0428260A2 (fr) * 1989-10-03 1991-05-22 Sanwa Laboratory Ltd. Agents de traitement de surfaces métalliques
EP0428383A1 (fr) * 1989-11-13 1991-05-22 Shikoku Chemicals Corporation Procédé pour le traitement de surface de cuivre ou d'alliage de cuivre
JPH04173983A (ja) * 1990-11-07 1992-06-22 Shikoku Chem Corp 銅及び銅合金の表面処理方法
JPH04183874A (ja) * 1990-11-17 1992-06-30 Shikoku Chem Corp 銅及び銅合金の表面処理方法
JPH0593281A (ja) * 1991-09-24 1993-04-16 Hideaki Yamaguchi 金属の表面処理方法
EP0551112A1 (fr) * 1992-01-08 1993-07-14 MEC CO., Ltd. Dérivé de la benzimidazole et une composition le contenant pour traiter les surfaces de cuivre ou les alliages de cuivre
JPH05230674A (ja) * 1992-02-24 1993-09-07 Hideaki Yamaguchi 金属の表面処理方法
EP0627499A1 (fr) * 1993-05-10 1994-12-07 Shikoku Chemicals Corporation Agent de traitement de surfaces en cuivre ou ses alliages

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3933531A (en) * 1972-04-11 1976-01-20 Natsuo Sawa Method of rust-preventing for copper and copper alloy
DE2557269A1 (de) * 1975-12-19 1977-06-30 Licentia Gmbh Verfahren zum aetzen von kupfer oder kupferlegierungen
JP3387528B2 (ja) * 1992-08-07 2003-03-17 朝日化学工業株式会社 銅または銅合金のエッチング用組成物およびそのエッチング方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0364132A1 (fr) * 1988-09-29 1990-04-18 Shikoku Chemicals Corporation Procédé pour former un revêtement de conversion sur une surface de cuivre ou d'un alliage de cuivre
EP0428260A2 (fr) * 1989-10-03 1991-05-22 Sanwa Laboratory Ltd. Agents de traitement de surfaces métalliques
EP0428383A1 (fr) * 1989-11-13 1991-05-22 Shikoku Chemicals Corporation Procédé pour le traitement de surface de cuivre ou d'alliage de cuivre
JPH04173983A (ja) * 1990-11-07 1992-06-22 Shikoku Chem Corp 銅及び銅合金の表面処理方法
JPH04183874A (ja) * 1990-11-17 1992-06-30 Shikoku Chem Corp 銅及び銅合金の表面処理方法
JPH0593281A (ja) * 1991-09-24 1993-04-16 Hideaki Yamaguchi 金属の表面処理方法
EP0551112A1 (fr) * 1992-01-08 1993-07-14 MEC CO., Ltd. Dérivé de la benzimidazole et une composition le contenant pour traiter les surfaces de cuivre ou les alliages de cuivre
JPH05230674A (ja) * 1992-02-24 1993-09-07 Hideaki Yamaguchi 金属の表面処理方法
EP0627499A1 (fr) * 1993-05-10 1994-12-07 Shikoku Chemicals Corporation Agent de traitement de surfaces en cuivre ou ses alliages

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
BAKSZT M.: "Providing Solderability Retention by Means of Chemical Inhibitors", METAL FINISHING, vol. 83, no. 1, 1 January 1985 (1985-01-01), HACKENSACK (DE), pages 35 - 38, XP002103089 *
CHEMICAL ABSTRACTS, vol. 119, no. 14, 4 October 1993, Columbus, Ohio, US; abstract no. 144612z, YAMAGUCHI: "Surface treatment of metals for corrosion prevention and heat resistance" page 347; *
PATENT ABSTRACTS OF JAPAN vol. 016, no. 479 (C - 0992) 6 October 1992 (1992-10-06) *
PATENT ABSTRACTS OF JAPAN vol. 016, no. 501 (C - 0996) 16 October 1992 (1992-10-16) *
PATENT ABSTRACTS OF JAPAN vol. 017, no. 693 (C - 1144) 17 December 1993 (1993-12-17) *

Cited By (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5800859A (en) * 1994-12-12 1998-09-01 Price; Andrew David Copper coating of printed circuit boards
US5807493A (en) * 1995-08-01 1998-09-15 Mec Co., Ltd. Microetching method for copper or copper alloy
EP0757118A1 (fr) * 1995-08-01 1997-02-05 MEC CO., Ltd. Composition pour la micro-gravure du cuivre ou ses alliages
EP0791671A1 (fr) * 1996-02-26 1997-08-27 Shikoku Chemicals Corporation Agent de traitement de surfaces en cuivre ou ses alliages
EP0844809A3 (fr) * 1996-11-20 1999-12-01 Ibiden Co, Ltd. Composition d'un masque de soudure et des panneaux à circuit imprimé
EP1802186A3 (fr) * 1996-11-20 2007-09-19 Ibiden Co., Ltd. Composition de masque de soudure et de panneaux à circuit imprimé
EP0887439A1 (fr) * 1997-06-12 1998-12-30 Macdermid Incorporated Procédé pour améliorer l'adhérence de polymères à des surfaces métalliquesl
US6146701A (en) * 1997-06-12 2000-11-14 Macdermid, Incorporated Process for improving the adhension of polymeric materials to metal surfaces
US6162503A (en) * 1997-06-12 2000-12-19 Macdermid, Incorporated Process for improving the adhesion of polymeric materials to metal surfaces
EP0893947A1 (fr) * 1997-07-24 1999-01-27 MEC CO., Ltd. Méthode pour le traitement de furface du cuivre ou d'alliage de cuivre
US6106899A (en) * 1997-07-24 2000-08-22 Mec Company Limited Method for surface treatment of copper or copper alloys
EP0926265A1 (fr) * 1997-12-19 1999-06-30 McGean-Rohco, Inc. Procédé et compositions pour la fabrication de surfaces de cuivre ayant une adhérence amélioré et articles produits à partir de ces surfaces
US6579591B2 (en) 1997-12-19 2003-06-17 Atotech Deutschland Gmbh Method of producing copper surfaces for improved bonding, compositions used therein and articles made therefrom
US6284309B1 (en) 1997-12-19 2001-09-04 Atotech Deutschland Gmbh Method of producing copper surfaces for improved bonding, compositions used therein and articles made therefrom
US6602440B2 (en) 1997-12-19 2003-08-05 Atotech Deutschland Gmbh Method of producing copper surfaces for improved bonding, compositions used therein and articles made therefrom
WO1999040765A1 (fr) * 1998-02-03 1999-08-12 Atotech Deutschland Gmbh Procede destine au pretraitement de surfaces de cuivre
WO1999040764A1 (fr) * 1998-02-03 1999-08-12 Atotech Deutschland Gmbh Solution et procede destines au pretraitement de surfaces de cuivre
US6723385B1 (en) 1998-02-03 2004-04-20 Atotech Deutschland Gmbh Process for the preliminary treatment of copper surfaces
US8129151B2 (en) 1998-03-18 2012-03-06 Ajinomoto Co., Inc. L-glutamic acid-producing bacterium and method for producing L-glutamic acid
EP0984672A2 (fr) * 1998-08-31 2000-03-08 MacDermid, Incorporated Procédé de traitement de surfaces métalliques
EP0984672A3 (fr) * 1998-08-31 2001-08-08 MacDermid, Incorporated Procédé de traitement de surfaces métalliques
EP1031644A1 (fr) * 1999-02-25 2000-08-30 Shipley Company LLC Produits chimiques à base de thiazoles et de thiocarbamides à utiliser dans des solutions de décapage oxydantes
US6503566B2 (en) 2000-06-08 2003-01-07 Donald Ferrier Process for improving the adhesion of polymeric materials to metal surfaces
US6383272B1 (en) 2000-06-08 2002-05-07 Donald Ferrier Process for improving the adhesion of polymeric materials to metal surfaces
WO2001094033A1 (fr) * 2000-06-08 2001-12-13 Macdermid, Incorporated Procede permettant d'ameliorer l'adherence de materiaux polymeres sur des surfaces metalliques
US6419784B1 (en) 2000-06-21 2002-07-16 Donald Ferrier Process for improving the adhesion of polymeric materials to metal surfaces
US6554948B1 (en) 2000-08-22 2003-04-29 Donald Ferrier Process for improving the adhesion of polymeric materials to metal surfaces
EP1253813A1 (fr) * 2001-04-25 2002-10-30 Mec Company Ltd. Stratifié et méthode pour sa fabrication
KR100714171B1 (ko) * 2001-04-25 2007-05-02 멧쿠 가부시키가이샤 적층체 및 그 제조방법
EP2259665A1 (fr) * 2001-04-25 2010-12-08 Mec Company Ltd. Stratifié et méthode pour sa fabrication
EP1565593A4 (fr) * 2002-11-26 2010-01-20 Macdermid Inc Procede permettant d'ameliorer l'adherence de materiaux polymeres a des surfaces metalliques
EP1565593A1 (fr) * 2002-11-26 2005-08-24 MacDermid, Incorporated Procede permettant d'ameliorer l'adherence de materiaux polymeres a des surfaces metalliques
EP1500719A1 (fr) 2003-07-25 2005-01-26 Mec Company Ltd. Solution de décapage, solution de remontage et méthode pour fabriquer des cablages en cuivre
US7431861B2 (en) 2003-07-25 2008-10-07 Mec Company Ltd. Etchant, replenishment solution and method for producing copper wiring using the same
CN100459068C (zh) * 2003-07-25 2009-02-04 Mec株式会社 蚀刻剂、补充液以及用它们制造铜布线的方法
EP2226410A1 (fr) * 2003-07-25 2010-09-08 Mec Company Ltd. Solution de décapage, solution de remontage et méthode pour fabriquer des cablages en cuivre
EP1795296A4 (fr) * 2004-08-31 2009-08-19 Senju Metal Industry Co Flux pour brasage
EP1795296A1 (fr) * 2004-08-31 2007-06-13 Senju Metal Industry Co., Ltd. Flux pour brasage
WO2006025224A1 (fr) 2004-08-31 2006-03-09 Senju Metal Industry Co., Ltd Flux pour brasage
US8404057B2 (en) 2004-08-31 2013-03-26 Senju Metal Industry Co., Ltd. Soldering flux
WO2008048240A3 (fr) * 2005-09-22 2008-08-14 Pantheon Chemical Inc agent chélateur de cuivre, composition comprenant l'agent et procédé de formation et d'utilisation de l'agent et de la composition
WO2008048240A2 (fr) * 2005-09-22 2008-04-24 Pantheon Chemical, Inc. agent chélateur de cuivre, composition comprenant l'agent et procédé de formation et d'utilisation de l'agent et de la composition
EP2514853A2 (fr) * 2011-04-18 2012-10-24 Mec Company Ltd. Composition liquide de formation de revêtement et procédé de formation de revêtement associé
EP2514853A3 (fr) * 2011-04-18 2014-11-05 Mec Company Ltd. Composition liquide de formation de revêtement et procédé de formation de revêtement associé
CN110527996A (zh) * 2019-09-27 2019-12-03 苏州天承化工有限公司 一种棕化液及其制备方法和应用

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US5532094A (en) 1996-07-02
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DE69516741T2 (de) 2000-08-31
DE69516741D1 (de) 2000-06-15
SG59906A1 (en) 1999-02-22
EP0670379B1 (fr) 2000-05-10
KR950032710A (ko) 1995-12-22
CN1117090A (zh) 1996-02-21

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